Multiple-State Emissions from Neat,Single-Component Molecular Solids: Suppression of Kasha's Rule

Three rigid and structurally simple heterocyclic stilbene derivatives, (E)-3H,3′H-[1,1′-biisobenzofuranylidene]-3,3′-dione, (E)-3-(3-oxobenzo[c] thiophen-1(3H)-ylidene)isobenzofuran-1(3H)-one, and (E)-3H,3′H-[1,1′-bibenzo[c] thiophenylidene]-3,3′-dione, are found to fluoresce in their neat solid phases, from upper (S₂) and lowest (S₁) singlet excited states, even at room temperature in air. Photophysical studies, single-crystal structures, and theoretical calculations indicate that large energy gaps between S₂ and S₁ states (T₂ and T₁ states) as well as an abundance of intra and intermolecular hydrogen bonds suppress internal conversions of the upper excited states in the solids and make possible the fluorescence from S₂ excited states (phosphorescence from T₂ excited states). These results, including unprecedented fluorescence quantum yields (2.3–9.6 %) from the S₂ states in the neat solids, establish a unique molecular skeleton for achieving multi-colored emissions from upper excited states by “suppressing” Kasha's rule.     

Stiff-stilbene derivatives as new bright fluorophores with aggregation-induced emission

Stiff-stilbene derivatives have been widely explored as molecular rotors, molecular force probes and optical switches with excellent performance. However, their function as fluorophores is poorly understood. In the present work, we design three stiffstilbene derivatives and study their photophysical properties. These compounds exhibit very weak emission in solution but significantly enhanced monomer emission in viscous solvent, bright excimer emission in aggregates and at solid state. Detailed spectroscopic studies, single crystal structural analysis, powder X-ray diffraction(XRD) as well as effects of substituents have been carefully examined. They provide direct evidence that intermolecular interactions and molecular packing, which can restrict bond vibration and rotation, are responsible for the bright aggregation-induced emission.